US6121344A - Optimum particle sized hybrid composite - Google Patents
Optimum particle sized hybrid composite Download PDFInfo
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- US6121344A US6121344A US09/270,999 US27099999A US6121344A US 6121344 A US6121344 A US 6121344A US 27099999 A US27099999 A US 27099999A US 6121344 A US6121344 A US 6121344A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/832—Nanostructure having specified property, e.g. lattice-constant, thermal expansion coefficient
- Y10S977/834—Optical properties of nanomaterial, e.g. specified transparency, opacity, or index of refraction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/902—Specified use of nanostructure
- Y10S977/904—Specified use of nanostructure for medical, immunological, body treatment, or diagnosis
- Y10S977/919—Dental
Definitions
- the present invention is generally related to a composite resin material used for dental restoration, and more particularly to a universal composite resin material suitable for all dental restorations incorporating a uniformly dispersed submicron sized reinforcing particulate which provides high strength, improved wear resistance and gloss retention in clinical use.
- Composite resins are a type of restorative material which are suspensions of strengthening agents, such as mineral filler particles, in a resin matrix. These materials may be dispersion reinforced, particulate reinforced, or hybrid composites.
- Dispersion reinforced composites include a reinforcing filler of, for example, fumed silica having a mean particle size of about 0.05 ⁇ m or less, with a filler loading of about 30%-45% by volume. Because of the small particle size and high surface area of the filler, the filler loading into the resin is limited by the ability of the resin to wet the filler. Consequently, the filler loading is limited to about 45% by volume. Due to the low loading, the filler particles are not substantially in contact with one another. Thus, the primary reinforcing mechanism of such dispersion reinforced composites is by dislocation of flaws in the matrix around the filler. In dispersion reinforced materials, the strength of the resin matrix contributes significantly to the total strength of the composite.
- dispersion reinforced composite resins or microfills are typically used for cosmetic restorations due to their ability to retain surface luster.
- these microfill resins use free radical-polymerizable resins such as methacrylate monomers, which, after polymerization, are much weaker than the dispersed filler.
- methacrylate monomers which, after polymerization, are much weaker than the dispersed filler.
- microfill resins are structurally weak, limiting their use to low stress restorations.
- HELIOMOLAR® is a dental composite including fumed silica particles on the order of 0.05 ⁇ m mean particle size and rare earth fluoride particle on the order of less than 0.2 ⁇ m mean particle size.
- HELIOMOLAR® is a radiopaque microfill-type composite. The rare earth fluoride particles contribute to both flexural strength and radiopacity.
- Particulate reinforced composites typically include a reinforcing filler having an average particle size greater than about 0.6 ⁇ m and a filler loading of about 60% by volume. At these high filler loadings, the filler particles begin to contact one another and contribute substantially to the reinforcing mechanism due to the interaction of the particles with one another and to interruption of flaws by the particles themselves. These particulate reinforced composite resins are stronger than microfill resins. As with the dispersion reinforced composites, the resin matrix typically includes methacrylate monomers. However, the filler in particulate reinforced composites has a greater impact on the total strength of the composite. Therefore, particulate reinforced composites are typically used for stress bearing restorations.
- Hybrid composite resins contain fillers having an average particle size of 0.6 ⁇ m or greater with a microfiller having an average particle size of about 0.05 ⁇ m or less.
- HERCULITE® XRV Kelr Corp.
- HERCULITE® is considered by many as an industry standard for hybrid composites. It has an average particle size of 0.84 ⁇ m and a filler loading of 57.5% by volume. The filler is produced by a wet milling process that produces fine particles that are substantially contaminant free. About 10% of this filler exceeds 1.50 ⁇ m in average particle size.
- the surface of HERCULITE® turns to a semi-glossy matte finish over time. Because of this, the restoration may become distinguishable from normal tooth structure when dry, which is not desirable for a cosmetic restoration.
- Another class of composites have a volume fraction of structural filler of about 10% to about 30% by volume. These flowable composites are mainly used in low viscosity applications to obtain good adaptation and to prevent the formation of gaps during the filling of a cavity.
- the particle size range includes particle sizes up to 1.0 ⁇ m and thus a dental composite using such filler will not provide a glossy surface in clinical use.
- the particles formed by the sol-gel process are spherical as shown in FIGS. 2A and 2B.
- the formulations described are designed to improve mechanical performance, wear and surface roughness of restorations, but do not provide for the retention of surface gloss in clinical use.
- Clinical studies of this material have actually shown high wear rates of 22.4 ⁇ m per year, which cannot establish a stable surface (S. Inokoshi, "Posterior Restorations: Ceramics or Composites?” in Transactions Third International Congress on Dental Materials Ed. H. Nakajima, Y. Tani JSDMD 1997).
- Communication by a milling method may also be used for forming the submicron particles.
- the predominant types of milling methods are dry milling and wet milling. In dry milling, air or an inert gas is used to keep particles in suspension. However, fine particles tend to agglomerate in response to van der Waals forces, which limits the capabilities of dry milling.
- Wet milling uses a liquid such as water or alcohol to control reagglomeration of fine particles. Therefore, wet milling is typically used for communication of submicron-sized particles.
- a wet mill typically includes spherical media that apply sufficient force to break particles that are suspended in a liquid medium. Milling devices are categorized by the method used to impart motion to the media. The motion imparted to wet ball mills includes tumbling, vibratory, planetary and agitation. While it is possible to form submicron particles with each of these types of mills, the agitation or agitator ball mill is typically most efficient.
- the agitator ball mill also known as an attrition or stirred mill, has several advantages including high energy efficiency, high solids handling, narrow size distribution of the product output, and the ability to produce homogeneous slurries.
- the major variables in using an agitator ball mill are agitator speed, suspension flow rate, residence time, slurry viscosity, solid size of the in-feed, milling media size and desired product size.
- agitator mills typically grind particles to a mean particle size approximately 1/1000 of the size of the milling media in the most efficient operation. In order to obtain mean particle sizes on the order of 0.05 ⁇ m to 0.5 ⁇ m, milling media having a size of less than 0.45 mm can be used.
- Milling media having diameters of 0.2 mm and about 0.6 mm are also available from Tosoh Ceramics, Bound Brook, N.J. Thus, to optimize milling, it is desired to use a milling media approximately 1000 times the size of the desired particle. This minimizes the time required for milling.
- YTZ yttria stabilized zirconia
- TZP tetragonal zirconia polycrystal
- Y-TZP has a fine grain, high strength and a high fracture toughness.
- YTZ is the hardest ceramic and because of this high hardness, the YTZ will not structurally degenerate during milling.
- High strength Y-TZP is formed by sintering at temperatures of about 1550° C.
- Y-TZP provides a suitable milling media for providing relatively pure structural fillers having mean particle sizes less than 0.5 ⁇ m.
- the present invention provides a resin-containing dental composite including a structural filler of ground particles having an average particle size of between about 0.05 ⁇ m and about 0.5 ⁇ m that has the high strength required for load bearing restorations, yet maintains a glossy appearance in clinical use required for cosmetic restorations. Further, because the structural filler particles are ground, the particles are nonspherical, providing increased adhesion of the resin to the structural filler, thereby further enhancing the overall strength of the composite. Through the use of structural filler particles that are ground and that have an average particle size less than the wavelength of light, that is less than about 0.50 ⁇ m, the dental composite of the present invention provides the luster and translucency required for cosmetic restorations.
- the surface of a dental restoration will reflect more light in some directions than in others even after wear of the composite by brushing.
- the visible light waves do not substantially interact with the structural filler particles protruding out of the surface of the composite, and therefore, haze is reduced and the luster of the surface is maintained even after substantial brushing.
- a known method of milling, agitator milling has been adapted for use in the field of dental composites.
- this method is capable of further reducing the average particle size of the HERCULITE® filler to an average particle size of between about 0.05 ⁇ m and 0.5 ⁇ m.
- the particle size is at or below the wavelength of light, which minimizes interaction with light, thus producing a stable glossy surface in clinical use.
- the particles are still large enough to reinforce the composite by the particulate reinforcement mechanism, so the restorations are also stress bearing.
- the number of larger particles, above 0.5 ⁇ m in diameter are also minimized to help produce the stable glossy surface.
- the structural filler particles are ground to an average particle size between about 0.05 ⁇ m and about 0.50 ⁇ m, the particles interact with one another to strengthen the composite, in the manner of typical hybrid composites, to allow a composite of the present invention to be useful in stress bearing restorations.
- the structural filler is ground, typically by agitator milling, to the preferred mean particle size.
- the grinding of the structural filler results in nonspherical particles which due to their irregular shape interact with the polymerized resin to a much greater extent to increase adhesion of the resin to the structural filler and thereby increase the overall strength of the composite.
- the irregular shape of the particles is shown in FIGS. 1A and 1B.
- Agitator milling with selected media and optimized parameters produces the required size particles, free of contamination in a narrow particle size distribution. This reduces the small percentage of particles above 0.5 ⁇ m which can contribute to producing a non-glossy surface in clinical use.
- microfill particles having an average particle size less than about 0.05 ⁇ m are added, preferably between about 1% by weight and about 15% by weight of the composite.
- the microfill particles contribute to dispersion reinforcement, fill the interstices between the larger structural filler particles reducing occluded volume, and provide a large surface area to be wetted by the resin to increase strength.
- the microfill particles also contribute to the flow properties of the uncured resin.
- FIG. 1A is a scanning electron micrograph, at 20,000 ⁇ magnification, of the ground particulate of the present invention.
- FIG. 1B is a scanning electron micrograph, at 5,0000 ⁇ magnification, of the ground particulate of the present invention.
- FIG. 2A is a scanning electron micrograph, at 20,000 ⁇ magnification, of the prior art filler particles formed by sol-gel processes.
- FIG. 2B is a scanning electron micrograph, at 100,000 ⁇ magnification, of the prior art filler particles formed by sol-gel processes.
- the present invention in a preferred form, is a dental restorative composite which includes a ground structural filler having a mean particle size between about 0.05 ⁇ m and about 0.50 ⁇ m and a microfill having a mean particle size less than about 0.05 ⁇ m in a curable resin, preferably a photopolymerizable resin containing methacrylate monomers.
- a curable resin preferably a photopolymerizable resin containing methacrylate monomers.
- methacrylate monomer resins are cured when exposed to blue visible light.
- the dental composite is applied to teeth by the dental practitioner and exposed to a visible light source to cure the resin.
- the cured resin has a flexural strength higher than 100 MPa which allows for the use of the resin in stress bearing applications.
- Communication is preferably performed in an agitator mill and more preferably an agitator mill designed to minimize contamination, such as that described in U.S. Pat. No. 6,010,085 entitled "Agitator Mill and Method of Use for Low Contamination Grinding,” C. Angeletakis, filed on even date herewith and incorporated herein by reference in its entirety.
- Communication deagglomerates the structural filler particles by separating particles from clusters, decreases the size of the structural filler particles, eliminates large particles by breakage and increases the specific surface area of the structural filler particles by producing a large quantity of very fine particles. Size reduction with an agitator mill occurs due to a combination of impact with the milling media, abrasion with the milling media and attrition of the particles.
- Structural fillers suitable for use in the present invention include barium magnesium aluminosilicate glass, barium aluminoborosilicate glass, amorphous silica, silica-zirconia, silica-titania, barium oxide, quartz, alumina and other inorganic oxide particles.
- the filler material to be milled such as barium aluminoborosilicate glass (for example, type SP-345, Specialty Glass, Oldsmar Fla.), is charged into an agitator mill, such as a one-liter total capacity agitator mill from Draiswerke Inc., Mahwah, N.J., type PML-H/V, modified to include a clear polyurethane clad agitator and grinding chamber, a YTZ main seal and a YTZ gap separator as described in U.S. Pat. No. 6,010,085 entitled "Agitator Mill and Method of Use for Low Contamination Grinding," C. Angeletakis, filed on even date herewith and incorporated herein by reference in its entirety.
- an agitator mill such as a one-liter total capacity agitator mill from Draiswerke Inc., Mahwah, N.J., type PML-H/V, modified to include a clear polyurethane clad agitator and grinding chamber, a YTZ main
- Method A used milling media with a size of 0.65 mm and Method B used milling media with a size of 0.40 mm.
- the agitator mill was operated at a tip speed of 10 m/sec. for 3 hours.
- Method C the ground slurry of Method A was used, and the mill was then charged with 70% of its volume of 0.20 mm Y-TZP milling media, and the milling process was repeated for 1.5 hours.
- rough edges and facets were created on the structural filler particles by the impact with the milling media, abrasion with the milling media and attrition of the particles. Each of these edges provide an adhesion site for the resin which increases the overall strength of the cured composite.
- the mean particle size is measured, typically by laser scattering.
- Laser scattering is a method of measuring mean particle size by sensing the average relative angular intensity of scattered light. A beam of monochromatic light with a uniform wave front is directed at the sample, the light is diffracted or scattered by the particles and a detector is used to measure the relative average intensity of the scattered light at various angles. The mean particle size and size distribution may then be calculated from the relative average intensity.
- One such laser scattering device is disclosed in U.S. Pat. No. 5,610,712 to Schmitz et al., incorporated herein by reference in its entirety. For the present example, a Horiba Model 2A-910 Laser Scattering Mean Particle Size Analyzer was used.
- the particle size range of the structural fillers prepared by methods A, B and C are set forth in TABLE 1, as well as the particle size range for the PRODIGY® (Kerr Corp.) hybrid composite.
- TABLE 1 shows, for example, that for Method A, 10% by volume of the filler particles have a mean particle size of less than 0.40 ⁇ m; 50% by volume of the filler particles have a mean particle size less than 0.62 ⁇ m; and 90% by volume of the filler particles have a mean particle size less than 0.82 ⁇ m.
- the slurry was then dried at 110° C. and the dried cake was sieved through a 100 mesh (150 ⁇ m) plastic screen.
- the ground glass was then silanated by spraying in a V-blender with a 20% hydrolyzed solution of gamma-methacryloxypropyltrimethoxy-silane in water to make the powder hydrophobic.
- the loading of the silane in the filler was 2.5% by weight.
- the properly sized structural filler is combined with colloid sized particles, such as types of silica, alumina and silicates, for example silica zirconia or silica titania, the particles having a mean particle size less than 0.05 ⁇ m.
- colloid sized particles such as types of silica, alumina and silicates, for example silica zirconia or silica titania, the particles having a mean particle size less than 0.05 ⁇ m.
- hydrophobic fumed silica is used in an amount between 1-15 wt % of the final composition.
- it is possible to use two types of fumed silica such as TS-530 having an average particle size of 0.02 ⁇ m and OX-50 having an average particle size of 0.04 ⁇ m.
- the structural filler and the colloidal fillers are then combined with a light-curable resin base material which may include commercially available monomers containing methacrylate groups.
- a light-curable resin base material which may include commercially available monomers containing methacrylate groups.
- TABLE 2 lists the components of the resin that will be used in later examples. Pigments such as titanium dioxide may be added to control optical properties of the composite.
- Other monomers may be used in the resin composition, such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, diurethane dimethacrylate (Rohamere 6661-0, Huls America, Somerset, N.J.), trimethylolpropane trimethacrylate, glyceryl dimethacrylate, neopentylglycol dimethacrylate.
- diethylene glycol dimethacrylate triethylene glycol dimethacrylate
- tetraethylene glycol dimethacrylate 1,6-hexanediol dimethacrylate
- 1,12-dodecanediol dimethacrylate 1,12-dodecanediol dimethacrylate
- diurethane dimethacrylate Rohamere 6
- the resin is introduced into a planetary mixer thermostated at 50° C.
- the planetary mixer is then started and the filler containing the physically admixed components listed in TABLE 3 are added slowly over a period of 3 hours.
- the composite is subsequently mixed for another hour and then de-aerated under attenuated oxygen pressure.
- the OX-50 particles are AEROSIL® OX-50 fumed silica, available commercially from Degussa Corp., Ridgefield Park, N.J.
- the OX-50 particles have a surface area of 50 ⁇ 15 m 2 /g and an average agglomerated particle size of 40 nanometers.
- the OX-50 particle is greater than 99.8 wt % SiO 2 with traces of Al 2 O 3 , Fe 2 O 3 , TiO 2 and HCl.
- the OX-50 particles are then silanated by spraying in a V-blender with a 20% hydrolyzed solution of gamma-methacryloxypropyltrimethoxysilane in water to make the powder hydrophobic.
- the loading of the silane in the filler was 5% by weight.
- the CAB-0-SIL TS-530 treated fumed silica is a high purity silica treated with hexamethyldisilazane to make the particles extremely hydrophobic.
- the CAB-O-SIL particles are fumed silica produced by hydrolysis of silicon tetrachloride vapor in a flame of hydrogen and oxygen. Any hydrogen chloride adsorbed onto the CAB-O-SIL particle during the combustion process is reduced by a calcination (typically to less than 200 ppm HCl).
- the colloid filler particles contribute to dispersion reinforcement, fill the interstices between the larger structural filler particles which reduces occluded volume, provide a large surface area to be wetted by the resin and therefore increases strength.
- the use of the colloidal fillers reduces polymer shrinkage and allows a match between the modulus of elasticity and the coefficient of thermal expansion of the composite with that of the tooth.
- the improved adhesion coupled with the control of the polymer shrinkage, the modulus of elasticity and the coefficient of thermal expansion reduces micro-leakage of bacteria along the bond interface between the tooth and the cured dental composite.
- the surface of the tooth is prepared by removing any portion of the tooth enamel, and if necessary the dentin, that is decayed or damaged. A retention groove is then formed in the dentin if needed to maintain the restoration on the tooth. The practitioner then adds opacifiers and pigments to match the color of the composite with the color of the tooth. The composite is then built up on the surface of the tooth to replace any lost material. Once the practitioner is satisfied with the appearance of the restoration the composite is exposed to a visible light source to cure the resin and activate the adhesive by cross-linking the polymer matrix. After the composite has been cured, the surface is polished.
- the mean particle size of the structural filler is limited to less than the wavelength of light to prevent the structural filler from decreasing surface gloss after substantial brushing. However, it is expected that as the particle size is reduced below about 1 ⁇ m the strength needed for load bearing restorations demises due to increasing occluded volume of resin. Currently, it is believed that a mean particle size between about 0.05 ⁇ m and about 0.5 ⁇ m provides the best balance between optical and structural properties.
- a resin composite was prepared by mixing:
- silanated barium aluminoborosilicate SP-3405 structural filler having a mean particle size of 0.62 ⁇ m as prepared by Method A, discussed above;
- silanated OX-50 fumed silica having an average particle size of 0.04 ⁇ m
- TS-530 hydrophobic fumed silica having an average particle size of 0.02 ⁇ m.
- a resin composite was prepared by mixing:
- silanated barium alurninoborosilicate SP-3405 structural filler having a mean particle size of 0.47 ⁇ m as prepared by Method B, discussed above;
- silanated OX-50 fumed silica having an average particle size of 0.04 ⁇ m
- TS-530 hydrophobic fumed silica having an average particle size of 0.02 ⁇ m.
- a resin composite was prepared by mixing:
- silanated barium aluminum silicate SP345 structural filler having a mean particle size of 0.36 ⁇ m as prepared by Method C, discussed above;
- silanated OX-50 fumed silica having an average particle size of 0.04 ⁇ m
- TS-530 hydrophobic fumed silica having an average particle size of 0.02 ⁇ m.
- the properties of the dental composites of EXAMPLES A, B, and C are compared with the PRODIGY® hybrid composite.
- the hybrid composite (PRODIGY®) has a flexural strength over 100 MPa, which allows its use in stress bearing restorations.
- the composites of EXAMPLES A, B, and C each have a flexural strength above 100 MPa, approaching that of the PRODIGY® composite, which allows their use in stress bearing restorations.
- the flexural modulus for the composites of EXAMPLES A and C is 9,248 MPa, which approaches the modulus of the PRODIGY® composite.
- the Rockwell hardness which is similar for the four composites reported in TABLE 3, is an average of 3 measurements on the surface of a cylindrical sample 10 mm in diameter and 4 mm in height.
- the composites were light cured for 40 seconds and stored in water for 24 hours at 37° C. prior to the hardness measurement.
- the glossy appearance of the PRODIGY® material is lost leaving a matte finish as occurs in normal clinical use.
- the dental composite of the present invention provides a restoration having the high strength useful for load bearing restorations and also provides translucency and surface gloss, useful in cosmetic restorations. The gloss is apparent even after substantial wear as can be observed in a recall appointment 6 months or longer after the placement of the restoration.
- the dental composite of the present invention provides the luster and translucency of dispersion reinforced composites with the strength of hybrid composites.
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Abstract
Description
TABLE 1 ______________________________________ Mean Particle Sizes In Microns VOLUME PRODIGY ® A B C ______________________________________ 10% 0.42 μm 0.40 μm 0.27 μm 0.24 μm 50% 0.84 μm 0.62 μm 0.47 μm 0.36 μm 90% 1.50 μm 0.82 μm 0.76 μm 0.61 μm ______________________________________
TABLE 2 ______________________________________ RESIN COMPOSITION % COMPONENT BY WEIGHT ______________________________________ BisGMA (Bisphenol A Diglycidyl ether dimethacrylate) 3.0 Trethylene Glycol Dimethacrylate 24.7 Ethoxylated Bisphenol A Dimethacrylate 71.1 2-Ethylhexyl-4-(dimethylamino)benzoate 0.49 Camphorquinone 0.17 2-Hydroxy-4-methoxy Benzophenone 0.49 (BHT) Butylated Hydroxytoluene 0.05 ______________________________________
TABLE 3 __________________________________________________________________________ Physical Properties of Small Particle Composites (SD) EXAMPLE EXAMPLE EXAMPLE PRODIGY ® A B C __________________________________________________________________________ Resin wt % 23 27.6 28.2 29.2 Mean Particle Size of 0.84 μm 0.6 μm 0.47 μm 0.35 μm Ground Filler Ground Barium aluminum 69.4 63.7 64.7 65.2 silicate, SP-345, wt % 40 nm silanated Silica, 3.5 5 3.1 2.3 OX-50, wt % 20 nm hydrophobic Silica, 4.1 3.7 3.9 3.3 TS-530, wt % Load Weight % 77 72.4 71.8 70.8 Load Volume % 57.5 51.6 50.7 49.3 Flexural Strength (MPa) 136 122 105 111 (18) (9) (14) (7) Flexural Modulus (MPa) 10,960 9,248 8801 9,248 (744) (522) (720) (522) Compressive Strength 367 366 312 368 (MPa) (52) (23) (40) (42) Rockwell Hardness 15T 83.3 80.1 80.4 77.5 Depth of Cure 40 s (mm) 5.5 4.7 4.3 4.3 Consistency-Slump (cm) 2.5 2.7 1.6 1.7 Gloss, 60 degrees 19.6 30.1 46.7 45.8 (0.3) (0.8) (0.3) (0.1) __________________________________________________________________________
TABLE 4 __________________________________________________________________________ Physical Property Comparison of Fine Particle Composite with Commercial Composites (SD) PALFIQUE SILUX EXAMPLE ESTELITE ® HELIOMOLAR ® PLUS ® DURAFIL ® B (TOKOYAMA) (VIVADENT) (3M) (KULZER) __________________________________________________________________________ Load Weight % 71.8 69 67 ca50 ca50 Load Volume % 50.7 ca45 44 ca38 ca38 Flexural Strength (MPa) 105 78 92 79 83 (14) (8) (13) (10) (12) Flexural Modulus (MPa) 8801 6690 6,277 7,000 5,325 (720) (500) (388) (639) (301) Compressive Strength (MPa) 312 357 279 248 428 (40) (25) (81) (96) (47) Rockwell Hardness 15T 80.4 80.6 77.0 81.7 76.9 Depth of Cure 40 s (mm) 4.3 4.2 4.4 4.4 5.5 Consistency-Slump (cm) 1.6 2.7 4.3 2.7 Gloss, 60 degrees 46.7 46.9 40.4 41.4 41.5 (0.3) (0.2) (0.5) (0.5) (1.1) Radiopacity (% Al) 210 175 200 0 0 __________________________________________________________________________
Claims (18)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/270,999 US6121344A (en) | 1998-06-19 | 1999-03-17 | Optimum particle sized hybrid composite |
US09/306,628 US6300390B1 (en) | 1998-06-09 | 1999-05-06 | Dental restorative composite |
DE69921943T DE69921943T2 (en) | 1998-06-19 | 1999-05-26 | Hybrid composite containing particles of optimal size |
CN99800986A CN1112909C (en) | 1998-06-19 | 1999-05-26 | Optimum particle sized hybrid composite |
PCT/US1999/011618 WO1999065453A1 (en) | 1998-06-19 | 1999-05-26 | Optimum particle sized hybrid composite |
EP99925867A EP1005318B1 (en) | 1998-06-19 | 1999-05-26 | Optimum particle sized hybrid composite |
AU42069/99A AU4206999A (en) | 1998-06-19 | 1999-05-26 | Optimum particle sized hybrid composite |
BR9906530-4A BR9906530A (en) | 1998-06-19 | 1999-05-26 | Dental composite |
JP2000554333A JP2002518309A (en) | 1998-06-19 | 1999-05-26 | Hybrid composites with optimal particle size |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US8985998P | 1998-06-19 | 1998-06-19 | |
US09/270,999 US6121344A (en) | 1998-06-19 | 1999-03-17 | Optimum particle sized hybrid composite |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/093,778 Continuation-In-Part US6127450A (en) | 1998-06-09 | 1998-06-09 | Dental restorative composite |
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US6121344A true US6121344A (en) | 2000-09-19 |
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Family Applications (1)
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US (1) | US6121344A (en) |
EP (1) | EP1005318B1 (en) |
JP (1) | JP2002518309A (en) |
CN (1) | CN1112909C (en) |
AU (1) | AU4206999A (en) |
BR (1) | BR9906530A (en) |
DE (1) | DE69921943T2 (en) |
WO (1) | WO1999065453A1 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US6232367B1 (en) * | 1999-10-07 | 2001-05-15 | Kerr Corporation | Opalescent fillers for dental restorative composites |
US6300390B1 (en) * | 1998-06-09 | 2001-10-09 | Kerr Corporation | Dental restorative composite |
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Citations (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US35264A (en) * | 1862-05-13 | Improvement in miners lamps | ||
US3792531A (en) * | 1970-12-28 | 1974-02-19 | Lee Pharmaceuticals | Dental restorative material of improved polishability |
US3893840A (en) * | 1972-09-06 | 1975-07-08 | Huber Corp J M | Amorphous precipitated siliceous pigments and methods for their production |
US4059232A (en) * | 1974-12-12 | 1977-11-22 | Draiswerke Gmbh | Stirring or agitating mills |
US4117981A (en) * | 1976-07-14 | 1978-10-03 | Draiswerke Gmbh | Stirring mill |
US4129261A (en) * | 1976-06-30 | 1978-12-12 | Draiswerke Gmbh | Agitating mill |
US4132806A (en) * | 1975-03-12 | 1979-01-02 | J. M. Huber Corporation | Novel precipitated siliceous products |
US4156766A (en) * | 1977-01-10 | 1979-05-29 | Johnson & Johnson | Acrylic polymerization systems and diacyl peroxide catalysts therefor |
US4177563A (en) * | 1977-06-25 | 1979-12-11 | Bayer Aktiengesellschaft | Dental filling material |
US4202813A (en) * | 1977-05-16 | 1980-05-13 | J. M. Huber Corporation | Rubber containing precipitated siliceous products |
US4215033A (en) * | 1978-09-08 | 1980-07-29 | American Dental Association Health Foundation | Composite dental material |
US4260454A (en) * | 1978-10-10 | 1981-04-07 | J. M. Huber Corporation | Precipitated siliceous products used in paper |
US4303205A (en) * | 1978-08-24 | 1981-12-01 | Gebruder Buhler Ag | Agitator mill and method of controlling the same |
US4336245A (en) * | 1975-03-12 | 1982-06-22 | J. M. Huber Corporation | Novel precipitated siliceous products and methods for their use and production |
US4375967A (en) * | 1980-10-21 | 1983-03-08 | Kulzer & Co. Gmbh | Dental composition containing X-ray opaque material |
US4380432A (en) * | 1980-09-03 | 1983-04-19 | Scientific Pharmaceuticals | Method for adhering structures to teeth |
US4422880A (en) * | 1975-03-12 | 1983-12-27 | J. M. Huber Corporation | Precipitated siliceous products |
US4496106A (en) * | 1981-02-19 | 1985-01-29 | Draiswerke Gmbh | Agitator-grinder |
US4503169A (en) * | 1984-04-19 | 1985-03-05 | Minnesota Mining And Manufacturing Company | Radiopaque, low visual opacity dental composites containing non-vitreous microparticles |
US4544359A (en) * | 1984-01-13 | 1985-10-01 | Pentron Corporation | Dental restorative material |
US4551486A (en) * | 1983-11-16 | 1985-11-05 | Dentsply Research & Development Corp. | Interpenetrating polymer network compositions |
US4558825A (en) * | 1982-05-25 | 1985-12-17 | Gebruder Netzsch Maschinenfabrik Gmbh & Co. | Agitator mill |
US4609687A (en) * | 1984-02-21 | 1986-09-02 | Bayer Aktiengesellschaft | Modified fillers for silicone dental pastes |
US4711913A (en) * | 1983-11-16 | 1987-12-08 | Dentsply International Inc. | Interpenetrating polymer network compositions employing rubber-modified polymers |
US4793809A (en) * | 1987-05-21 | 1988-12-27 | Myron International, Inc. | Fiber filled dental porcelain |
US4801528A (en) * | 1981-05-04 | 1989-01-31 | Dentsply Research & Development Corporation | Dental adhesive system |
US4813875A (en) * | 1984-07-31 | 1989-03-21 | Dentsply Research & Development Corp. | Chain extended urethane diacrylate and dental impression formation |
US4846165A (en) * | 1986-11-26 | 1989-07-11 | Dentsply Research & Development Corp. | Wound dressing membrane |
US4863977A (en) * | 1983-11-16 | 1989-09-05 | Dentsply Research & Development Corp. | Process for preparing interpenetrating polymer network objects employing rubber-modified polymers |
US4936775A (en) * | 1981-05-04 | 1990-06-26 | Dentsply Research & Development, Corp. | Dental adhesive system |
US4978640A (en) * | 1988-02-24 | 1990-12-18 | Massachusetts Institute Of Technology | Dispersion strengthened composite |
US5055497A (en) * | 1988-03-17 | 1991-10-08 | Kuraray Company, Ltd. | Curable resinous composition |
US5062577A (en) * | 1987-05-18 | 1991-11-05 | Draiswerke Gmbh | Agitator mill |
US5065946A (en) * | 1988-07-21 | 1991-11-19 | Matsushita Electric Industrial Co., Ltd. | Media agitating mill and method for milling ceramic powder |
US5133508A (en) * | 1990-01-30 | 1992-07-28 | Draiswerke Gmbh | Agitator mill |
US5177120A (en) * | 1984-07-31 | 1993-01-05 | Dentsply Research & Development Corp. | Chain extended urethane diacrylate and dental impression formation |
US5210109A (en) * | 1983-11-16 | 1993-05-11 | Dentsply Research & Development Corp. | Interpenetrating polymer network compositions employing rubber-modified polymers |
US5211748A (en) * | 1989-03-21 | 1993-05-18 | National Research Development Corporation | Identifiable dental restorative material |
US5218070A (en) * | 1991-02-11 | 1993-06-08 | Dentsply G.M.B.H. | Dental/medical composition and use |
US5221202A (en) * | 1991-04-12 | 1993-06-22 | James Jack L | Packaging and adhesive for predispensed orthodontic brackets |
US5335867A (en) * | 1991-07-09 | 1994-08-09 | Draiswerke Gmbh | Agitator mill |
US5338773A (en) * | 1993-04-19 | 1994-08-16 | Dentsply Research & Development Corp. | Dental composition and method |
US5502087A (en) * | 1993-06-23 | 1996-03-26 | Dentsply Research & Development Corp. | Dental composition, prosthesis, and method for making dental prosthesis |
USRE35264E (en) | 1981-05-04 | 1996-06-04 | Dentsply Research & Development Corp. | Dental adhesive system |
US5548000A (en) * | 1994-04-14 | 1996-08-20 | Heraeus Kulzer Gmbh | Artificial tooth |
US5547379A (en) * | 1994-10-06 | 1996-08-20 | Hasel; Robert W. | Method of restoring a tooth |
US5554030A (en) * | 1994-06-30 | 1996-09-10 | Minnesota Mining And Manufacturing Company | Method for bonding non-amalgam restorative materials to dental surfaces |
US5556038A (en) * | 1993-09-20 | 1996-09-17 | Showa Shell Sekiyu K.K. | Method for producing ultra fine particles |
US5595487A (en) * | 1994-06-30 | 1997-01-21 | Minnesota Mining And Manufacturing Company | Method for bonding amalgam to dental surfaces |
US5604626A (en) * | 1995-02-10 | 1997-02-18 | Donnelly Corporation | Photochromic devices |
US5609675A (en) * | 1994-07-04 | 1997-03-11 | Tokuyama Corporation | Inorganic composition |
US5610712A (en) * | 1993-06-04 | 1997-03-11 | Coulter Corporation | Laser diffraction particle sizing method using a monomode optical fiber |
US5612414A (en) * | 1993-11-05 | 1997-03-18 | Lanxide Technology Company, Lp | Organic/inorganic polymers |
US5616650A (en) * | 1993-11-05 | 1997-04-01 | Lanxide Technology Company, Lp | Metal-nitrogen polymer compositions comprising organic electrophiles |
US5710194A (en) * | 1993-04-19 | 1998-01-20 | Dentsply Research & Development Corp. | Dental compounds, compositions, products and methods |
US5837752A (en) * | 1997-07-17 | 1998-11-17 | Massachusetts Institute Of Technology | Semi-interpenetrating polymer networks |
US5936006A (en) * | 1996-04-26 | 1999-08-10 | Ivoclar Ag | Filled and polymerizable dental material |
US5990195A (en) * | 1997-05-26 | 1999-11-23 | Gc Corporation | Dental resin material and process for producing the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2403211C3 (en) * | 1974-01-23 | 1981-12-24 | Etablissement Dentaire Ivoclar, Schaan | Material for dental purposes |
US4859716A (en) * | 1987-11-06 | 1989-08-22 | Den-Mat Corporation | Microfilled dental composite and method for making it |
DE4029230C2 (en) | 1990-09-14 | 1995-03-23 | Ivoclar Ag | Polymerizable dental material |
DK0486775T3 (en) * | 1990-11-17 | 1995-03-13 | Heraeus Kulzer Gmbh | Polymerizable dental material |
-
1999
- 1999-03-17 US US09/270,999 patent/US6121344A/en not_active Expired - Lifetime
- 1999-05-26 WO PCT/US1999/011618 patent/WO1999065453A1/en active IP Right Grant
- 1999-05-26 AU AU42069/99A patent/AU4206999A/en not_active Abandoned
- 1999-05-26 CN CN99800986A patent/CN1112909C/en not_active Expired - Fee Related
- 1999-05-26 BR BR9906530-4A patent/BR9906530A/en not_active IP Right Cessation
- 1999-05-26 EP EP99925867A patent/EP1005318B1/en not_active Revoked
- 1999-05-26 DE DE69921943T patent/DE69921943T2/en not_active Expired - Lifetime
- 1999-05-26 JP JP2000554333A patent/JP2002518309A/en active Pending
Patent Citations (66)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US35264A (en) * | 1862-05-13 | Improvement in miners lamps | ||
US3792531A (en) * | 1970-12-28 | 1974-02-19 | Lee Pharmaceuticals | Dental restorative material of improved polishability |
US3893840A (en) * | 1972-09-06 | 1975-07-08 | Huber Corp J M | Amorphous precipitated siliceous pigments and methods for their production |
US4059232A (en) * | 1974-12-12 | 1977-11-22 | Draiswerke Gmbh | Stirring or agitating mills |
US4422880A (en) * | 1975-03-12 | 1983-12-27 | J. M. Huber Corporation | Precipitated siliceous products |
US4336245A (en) * | 1975-03-12 | 1982-06-22 | J. M. Huber Corporation | Novel precipitated siliceous products and methods for their use and production |
US4132806A (en) * | 1975-03-12 | 1979-01-02 | J. M. Huber Corporation | Novel precipitated siliceous products |
US4157920A (en) * | 1975-03-12 | 1979-06-12 | J. M. Huber Corporation | Novel precipitated siliceous products and methods for their use and production |
US4161455A (en) * | 1975-03-12 | 1979-07-17 | J. M. Huber Corporation | Novel precipitated siliceous products and methods for their use and production |
US4129261A (en) * | 1976-06-30 | 1978-12-12 | Draiswerke Gmbh | Agitating mill |
US4117981A (en) * | 1976-07-14 | 1978-10-03 | Draiswerke Gmbh | Stirring mill |
US4156766A (en) * | 1977-01-10 | 1979-05-29 | Johnson & Johnson | Acrylic polymerization systems and diacyl peroxide catalysts therefor |
US4202813A (en) * | 1977-05-16 | 1980-05-13 | J. M. Huber Corporation | Rubber containing precipitated siliceous products |
US4177563A (en) * | 1977-06-25 | 1979-12-11 | Bayer Aktiengesellschaft | Dental filling material |
US4303205A (en) * | 1978-08-24 | 1981-12-01 | Gebruder Buhler Ag | Agitator mill and method of controlling the same |
US4215033A (en) * | 1978-09-08 | 1980-07-29 | American Dental Association Health Foundation | Composite dental material |
US4260454A (en) * | 1978-10-10 | 1981-04-07 | J. M. Huber Corporation | Precipitated siliceous products used in paper |
US4380432A (en) * | 1980-09-03 | 1983-04-19 | Scientific Pharmaceuticals | Method for adhering structures to teeth |
US4375967A (en) * | 1980-10-21 | 1983-03-08 | Kulzer & Co. Gmbh | Dental composition containing X-ray opaque material |
US4496106A (en) * | 1981-02-19 | 1985-01-29 | Draiswerke Gmbh | Agitator-grinder |
US4936775A (en) * | 1981-05-04 | 1990-06-26 | Dentsply Research & Development, Corp. | Dental adhesive system |
US4801528A (en) * | 1981-05-04 | 1989-01-31 | Dentsply Research & Development Corporation | Dental adhesive system |
USRE35264E (en) | 1981-05-04 | 1996-06-04 | Dentsply Research & Development Corp. | Dental adhesive system |
US4558825A (en) * | 1982-05-25 | 1985-12-17 | Gebruder Netzsch Maschinenfabrik Gmbh & Co. | Agitator mill |
US4551486A (en) * | 1983-11-16 | 1985-11-05 | Dentsply Research & Development Corp. | Interpenetrating polymer network compositions |
US4711913A (en) * | 1983-11-16 | 1987-12-08 | Dentsply International Inc. | Interpenetrating polymer network compositions employing rubber-modified polymers |
US5210109A (en) * | 1983-11-16 | 1993-05-11 | Dentsply Research & Development Corp. | Interpenetrating polymer network compositions employing rubber-modified polymers |
US4863977A (en) * | 1983-11-16 | 1989-09-05 | Dentsply Research & Development Corp. | Process for preparing interpenetrating polymer network objects employing rubber-modified polymers |
US4544359A (en) * | 1984-01-13 | 1985-10-01 | Pentron Corporation | Dental restorative material |
US4609687A (en) * | 1984-02-21 | 1986-09-02 | Bayer Aktiengesellschaft | Modified fillers for silicone dental pastes |
US4503169A (en) * | 1984-04-19 | 1985-03-05 | Minnesota Mining And Manufacturing Company | Radiopaque, low visual opacity dental composites containing non-vitreous microparticles |
US4813875A (en) * | 1984-07-31 | 1989-03-21 | Dentsply Research & Development Corp. | Chain extended urethane diacrylate and dental impression formation |
US5177120A (en) * | 1984-07-31 | 1993-01-05 | Dentsply Research & Development Corp. | Chain extended urethane diacrylate and dental impression formation |
US4846165A (en) * | 1986-11-26 | 1989-07-11 | Dentsply Research & Development Corp. | Wound dressing membrane |
US5062577A (en) * | 1987-05-18 | 1991-11-05 | Draiswerke Gmbh | Agitator mill |
US4793809A (en) * | 1987-05-21 | 1988-12-27 | Myron International, Inc. | Fiber filled dental porcelain |
US4978640A (en) * | 1988-02-24 | 1990-12-18 | Massachusetts Institute Of Technology | Dispersion strengthened composite |
US5055497A (en) * | 1988-03-17 | 1991-10-08 | Kuraray Company, Ltd. | Curable resinous composition |
US5065946A (en) * | 1988-07-21 | 1991-11-19 | Matsushita Electric Industrial Co., Ltd. | Media agitating mill and method for milling ceramic powder |
US5211748A (en) * | 1989-03-21 | 1993-05-18 | National Research Development Corporation | Identifiable dental restorative material |
US5133508A (en) * | 1990-01-30 | 1992-07-28 | Draiswerke Gmbh | Agitator mill |
US5218070A (en) * | 1991-02-11 | 1993-06-08 | Dentsply G.M.B.H. | Dental/medical composition and use |
US5221202A (en) * | 1991-04-12 | 1993-06-22 | James Jack L | Packaging and adhesive for predispensed orthodontic brackets |
US5335867A (en) * | 1991-07-09 | 1994-08-09 | Draiswerke Gmbh | Agitator mill |
US5338773A (en) * | 1993-04-19 | 1994-08-16 | Dentsply Research & Development Corp. | Dental composition and method |
US5710194A (en) * | 1993-04-19 | 1998-01-20 | Dentsply Research & Development Corp. | Dental compounds, compositions, products and methods |
US5610712A (en) * | 1993-06-04 | 1997-03-11 | Coulter Corporation | Laser diffraction particle sizing method using a monomode optical fiber |
US5502087A (en) * | 1993-06-23 | 1996-03-26 | Dentsply Research & Development Corp. | Dental composition, prosthesis, and method for making dental prosthesis |
US5556038A (en) * | 1993-09-20 | 1996-09-17 | Showa Shell Sekiyu K.K. | Method for producing ultra fine particles |
US5733997A (en) * | 1993-11-05 | 1998-03-31 | Lanxide Technology Company, Lp | Metal-nitrogen polymer compositions comprising organic electrophiles |
US5637641A (en) * | 1993-11-05 | 1997-06-10 | Lanxide Technology Company, Lp | Metal-nitrogen polymer compositions comprising organic electrophiles |
US5807954A (en) * | 1993-11-05 | 1998-09-15 | Lanxide Technology Company, Lp | Metal-nitrogen polymer compositions comprising organic electrophiles |
US5767218A (en) * | 1993-11-05 | 1998-06-16 | Lanxide Technology Company, Lp | Metal-nitrogen polymer compositions comprising organic electrophiles |
US5750628A (en) * | 1993-11-05 | 1998-05-12 | Lanxide Technology Company, Lp | Metal-nitrogen polymer compositions comprising organic electrophiles |
US5612414A (en) * | 1993-11-05 | 1997-03-18 | Lanxide Technology Company, Lp | Organic/inorganic polymers |
US5616650A (en) * | 1993-11-05 | 1997-04-01 | Lanxide Technology Company, Lp | Metal-nitrogen polymer compositions comprising organic electrophiles |
US5548000A (en) * | 1994-04-14 | 1996-08-20 | Heraeus Kulzer Gmbh | Artificial tooth |
US5595487A (en) * | 1994-06-30 | 1997-01-21 | Minnesota Mining And Manufacturing Company | Method for bonding amalgam to dental surfaces |
US5554030A (en) * | 1994-06-30 | 1996-09-10 | Minnesota Mining And Manufacturing Company | Method for bonding non-amalgam restorative materials to dental surfaces |
US5609675A (en) * | 1994-07-04 | 1997-03-11 | Tokuyama Corporation | Inorganic composition |
US5547379A (en) * | 1994-10-06 | 1996-08-20 | Hasel; Robert W. | Method of restoring a tooth |
US5604626A (en) * | 1995-02-10 | 1997-02-18 | Donnelly Corporation | Photochromic devices |
US5838483A (en) * | 1995-02-10 | 1998-11-17 | Donnelly Corporation | Photochromic devices |
US5936006A (en) * | 1996-04-26 | 1999-08-10 | Ivoclar Ag | Filled and polymerizable dental material |
US5990195A (en) * | 1997-05-26 | 1999-11-23 | Gc Corporation | Dental resin material and process for producing the same |
US5837752A (en) * | 1997-07-17 | 1998-11-17 | Massachusetts Institute Of Technology | Semi-interpenetrating polymer networks |
Non-Patent Citations (8)
Title |
---|
Cabot Corporation, CAB O SIL TS 530 Treated Fumed Sllica, , Technical Data, Jul. 1989. * |
Cabot Corporation, CAB-O-SIL TS-530 Treated Fumed Sllica,, Technical Data, Jul. 1989. |
Degussa Corporation, Technical Data for AEROSIL Types (no date available). * |
Degussa Corporation, Technical Data for AEROSIL® Types (no date available). |
Dennis Miller, Cabot Corporation, CAB O SIL Fumed Silica Properties and Functions , pp. 3 5 (no date available). * |
Dennis Miller, Cabot Corporation, CAB-O-SIL® Fumed Silica Properties and Functions, pp. 3-5 (no date available). |
S. Inokoshi, "Posterior Restorations: Ceramics or Composites?", Transactions Third International Congress on Dental Materials, Ed. H. Nakajima, Y. Tani JSDMD (Nov. 1997). |
S. Inokoshi, Posterior Restorations: Ceramics or Composites , Transactions Third International Congress on Dental Materials, Ed. H. Nakajima, Y. Tani JSDMD (Nov. 1997). * |
Cited By (76)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6300390B1 (en) * | 1998-06-09 | 2001-10-09 | Kerr Corporation | Dental restorative composite |
US6232367B1 (en) * | 1999-10-07 | 2001-05-15 | Kerr Corporation | Opalescent fillers for dental restorative composites |
US7566412B2 (en) * | 1999-11-10 | 2009-07-28 | Dentsply International Inc. | Dental method and device |
US7476347B1 (en) * | 1999-11-10 | 2009-01-13 | Dentsply International, Inc. | Process for making denture having integral teeth and denture base |
US20080103229A1 (en) * | 2000-02-17 | 2008-05-01 | Uwe Walz | Dental composition with improved light stability |
US8026295B2 (en) | 2000-02-17 | 2011-09-27 | Dentsply International, Inc. | Dental composition with improved light stability |
US20040225029A1 (en) * | 2000-02-17 | 2004-11-11 | Uwe Walz | Dental composition with improved light stability |
US20040220291A1 (en) * | 2000-08-11 | 2004-11-04 | Uwe Walz | Polyaminoester and their application in dental compositions |
US20030105184A1 (en) * | 2000-08-11 | 2003-06-05 | Dentsply Detrey Gmbh | Polyaminoester and their application in dental compositions |
US20030130373A1 (en) * | 2000-08-11 | 2003-07-10 | Dentsply Detrey Gmbh | Dental compositions comprising bisacrylamides and use thereof |
US6734223B2 (en) | 2000-08-11 | 2004-05-11 | Dentsply Detrey Gmbh | Polyaminoester and their application in dental compositions |
US6767936B2 (en) | 2000-08-11 | 2004-07-27 | Dentsply Detrey Gmbh | Dental compositions comprising bisacrylamides and use thereof |
US20030225182A1 (en) * | 2001-01-04 | 2003-12-04 | Dentsply Detrey Gmbh | Dental composition with improved light stability |
US6890968B2 (en) | 2001-05-16 | 2005-05-10 | Kerr Corporation | Prepolymerized filler in dental restorative composite |
US20030032693A1 (en) * | 2001-05-16 | 2003-02-13 | Kerr Corporation | Prepolymerized filler in dental restorative composite |
US6593395B2 (en) * | 2001-05-16 | 2003-07-15 | Kerr Corporation | Dental composition containing discrete nanoparticles |
US20050267232A1 (en) * | 2001-08-13 | 2005-12-01 | Klee Joachim E | Dental root canal filling cones |
US20030045604A1 (en) * | 2001-08-13 | 2003-03-06 | Klee Joachim E. | Dental root canal filling cones |
US20030114553A1 (en) * | 2001-08-15 | 2003-06-19 | Naimul Karim | Hardenable self-supporting structures and methods |
US7674850B2 (en) | 2001-08-15 | 2010-03-09 | 3M Innovative Properties Company | Hardenable self-supporting structures and methods |
US7816423B2 (en) | 2001-08-15 | 2010-10-19 | 3M Innovative Properties Company | Hardenable self-supporting structures and methods |
US7750063B2 (en) | 2001-10-24 | 2010-07-06 | Pentron Clinical Technologies, Llc | Dental filling material |
US7837471B2 (en) | 2001-10-24 | 2010-11-23 | Pentron Clinical Technologies, Llc | Dental filling materials and methods of use |
US9492360B2 (en) | 2001-10-24 | 2016-11-15 | Pentron Clinical Technologies, Llc | Endodontic post and obturator |
EP1396254A1 (en) * | 2002-09-04 | 2004-03-10 | Kerr Corporation | Prepolymerized filler in dental restorative composite |
US20050226819A1 (en) * | 2002-09-27 | 2005-10-13 | Pierson Paul R | Packaged dental composition |
US20070041776A1 (en) * | 2002-09-27 | 2007-02-22 | Pierson Paul R | Packaged dental composition |
US20040171716A1 (en) * | 2002-12-03 | 2004-09-02 | Uwe Walz | Dental compositions comprising bisacrylamides and use thereof |
US20040209990A1 (en) * | 2003-04-15 | 2004-10-21 | Uwe Walz | Low shrinking polymerizable dental material |
US8136657B2 (en) | 2003-08-19 | 2012-03-20 | 3M Innovative Properties Company | Packaged hardenable dental article |
US7811486B2 (en) | 2003-08-19 | 2010-10-12 | 3M Innovative Properties Company | Method of manufacturing a hardenable dental article |
US20050040551A1 (en) * | 2003-08-19 | 2005-02-24 | Biegler Robert M. | Hardenable dental article and method of manufacturing the same |
US20050042577A1 (en) * | 2003-08-19 | 2005-02-24 | Kvitrud James R. | Dental crown forms and methods |
EP1570831A1 (en) * | 2004-03-02 | 2005-09-07 | Ernst Mühlbauer GmbH & Co.KG | Polymerisable dental material containing a filler |
WO2005084611A1 (en) * | 2004-03-02 | 2005-09-15 | Ernst Mühlbauer Gmbh & Co. Kg | Filled polymerisable dental material and method for the production thereof |
US20070142495A1 (en) * | 2004-03-02 | 2007-06-21 | Stephan Neffgen | Filled polymerisable dental material and method for the production thereof |
US20070184121A1 (en) * | 2004-03-30 | 2007-08-09 | Chien-Min Sung | Healthcare and cosmetic compositions containing nanodiamond |
US20050220829A1 (en) * | 2004-03-30 | 2005-10-06 | Chien-Min Sung | Healthcare and cosmetic compositions containing nanodiamond |
US8481007B2 (en) | 2004-03-30 | 2013-07-09 | Chien-Min Sung | Compositions and methods for providing ultraviolet radiation protection |
US7294340B2 (en) | 2004-03-30 | 2007-11-13 | Chien-Min Sung | Healthcare and cosmetic compositions containing nanodiamond |
US20080182948A1 (en) * | 2004-06-15 | 2008-07-31 | Xiaoming Jin | Low shrinkage and low stress dental compositions |
US20080182997A1 (en) * | 2004-06-15 | 2008-07-31 | Dentsply International Inc. | Radical polymerizable macrocyclic resin compositions with low polymerization stress |
US20110152569A1 (en) * | 2004-06-15 | 2011-06-23 | Xiaoming Jin | Radical polymerizable macrocyclic resin compositions with low polymerization stress |
US8461227B2 (en) | 2004-06-15 | 2013-06-11 | Dentsply International Inc. | Radical polymerizable macrocyclic resin compositions with low polymerization stress |
US20060287459A1 (en) * | 2004-06-15 | 2006-12-21 | Xiaoming Jin | Radical polymerizable macrocyclic resin compositions with low polymerization stress |
US8129446B2 (en) | 2004-06-15 | 2012-03-06 | Dentsply International Inc. | Radical polymerizable macrocyclic resin compositions with low polymerization stress |
US20070249752A1 (en) * | 2004-09-16 | 2007-10-25 | Kuraray Medical Inc. | Dental Polymerizable Core Build-Up Material of Separately Packed Type |
US7820733B2 (en) | 2004-09-16 | 2010-10-26 | Kuraray Medical Inc. | Dental polymerizable core build-up material of separately packed type |
US7795164B2 (en) | 2005-10-27 | 2010-09-14 | Ivoclar Vivadent Ag | Dental glass |
DE102005051387B3 (en) * | 2005-10-27 | 2007-01-25 | Ivoclar Vivadent Ag | Dental glass useful as a filler for dental composites comprises oxides of silicon, aluminum, magnesium, lanthanum, tungsten and zirconium |
US20090113936A1 (en) * | 2005-10-27 | 2009-05-07 | Ivoclar Vivadent Ag | Dental Glass |
US20090030109A1 (en) * | 2005-11-18 | 2009-01-29 | Hare Robert V | Dental composite restorative material |
US8647426B2 (en) | 2006-12-28 | 2014-02-11 | 3M Innovative Properties Company | Dental filler and methods |
US8735463B2 (en) | 2007-05-31 | 2014-05-27 | Creighton University | Self-healing dental composites and related methods |
US20100292363A1 (en) * | 2007-12-21 | 2010-11-18 | Ernst Mühlbauer Gmbh & Co. Kg | Material for building up stumps |
US8162665B2 (en) * | 2008-08-13 | 2012-04-24 | Kerr Corporation | Single-part, light-curable, self-adhering dental restorative composition and method of using the same |
US20100041786A1 (en) * | 2008-08-13 | 2010-02-18 | Kerr Corporation | Single-part, light-curable, self-adhering dental restorative composition and method of using the same |
US7946850B2 (en) * | 2008-08-13 | 2011-05-24 | Kerr Corporation | Single-part, light-curable, self-adhering dental restorative composition and method of using the same |
US20110217677A1 (en) * | 2008-08-13 | 2011-09-08 | Kerr Corporation | Single-part, light-curable, self-adhering dental restorative composition and method of using the same |
US20110196062A1 (en) * | 2008-10-15 | 2011-08-11 | Craig Bradley D | Fillers and Composite Materials with Zirconia and Silica Nanoparticles |
US8722759B2 (en) | 2008-10-15 | 2014-05-13 | 3M Innovative Properties Company | Fillers and composite materials with zirconia and silica nanoparticles |
US9642782B2 (en) * | 2011-05-27 | 2017-05-09 | Kerr Corporation | Dental restorative material |
US9237991B2 (en) * | 2011-05-27 | 2016-01-19 | Kerr Corporation | Dental restorative material |
EP2526921A2 (en) | 2011-05-27 | 2012-11-28 | Kerr Corporation | Dental restorative material |
US20120302662A1 (en) * | 2011-05-27 | 2012-11-29 | Kerr Corporation | Dental restorative material |
US8822564B2 (en) * | 2011-05-27 | 2014-09-02 | Kerr Corporation | Dental restorative material |
EP2526921A3 (en) * | 2011-05-27 | 2014-11-05 | Kerr Corporation | Dental restorative material |
US20140371342A1 (en) * | 2011-05-27 | 2014-12-18 | Kerr Corporation | Dental restorative material |
EP2537507A2 (en) | 2011-06-20 | 2012-12-26 | Kerr Corporation | Compositions dentaires contenant des fibres raccourcies |
EP2537507A3 (en) * | 2011-06-20 | 2013-09-04 | Kerr Corporation | Compositions dentaires contenant des fibres raccourcies |
US20160024334A1 (en) * | 2011-12-15 | 2016-01-28 | Dentsply International Inc. | Composite filler particles and process for the preparation thereof |
US10040969B2 (en) * | 2011-12-15 | 2018-08-07 | Dentsply Sirona Inc. | Composite filler particles and process for the preparation thereof |
EP2882802B1 (en) | 2012-08-10 | 2017-06-28 | Sika Technology AG | Weather-resistant silicon mixture with improved shape retention |
US9144533B2 (en) * | 2012-08-21 | 2015-09-29 | Heraeus Kulzer Gmbh | Dental adhesive agent for high-performance polymers |
US20140053965A1 (en) * | 2012-08-21 | 2014-02-27 | Heraeus Kulzer Gmbh | Dental adhesive agent for high-performance polymers |
US10261430B2 (en) * | 2016-01-14 | 2019-04-16 | Samsung Electronics Co., Ltd. | Photoreceptor for electrophotography and image forming apparatus employing the same |
Also Published As
Publication number | Publication date |
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WO1999065453A1 (en) | 1999-12-23 |
DE69921943D1 (en) | 2004-12-23 |
CN1112909C (en) | 2003-07-02 |
AU4206999A (en) | 2000-01-05 |
EP1005318B1 (en) | 2004-11-17 |
JP2002518309A (en) | 2002-06-25 |
DE69921943T2 (en) | 2005-12-01 |
BR9906530A (en) | 2000-07-18 |
CN1272781A (en) | 2000-11-08 |
EP1005318A1 (en) | 2000-06-07 |
WO1999065453A9 (en) | 2000-07-20 |
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